US10725328B2 - Temperature-controlled dimming film with a function of shielding near-infrared light and preparation method thereof - Google Patents

Temperature-controlled dimming film with a function of shielding near-infrared light and preparation method thereof Download PDF

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US10725328B2
US10725328B2 US16/466,457 US201716466457A US10725328B2 US 10725328 B2 US10725328 B2 US 10725328B2 US 201716466457 A US201716466457 A US 201716466457A US 10725328 B2 US10725328 B2 US 10725328B2
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liquid crystal
temperature
dimming film
polymerizable monomers
nanoparticles
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US20190310499A1 (en
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Huai Yang
Xiao Liang
Mei Chen
Shumeng GUO
Lanying Zhang
Cuihong Zhang
Qian Wang
Chenyue LI
Cheng Zou
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Beijing Zhijing Times Technology Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/1313—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells specially adapted for a particular application
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/132—Thermal activation of liquid crystals exhibiting a thermo-optic effect
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K2019/521—Inorganic solid particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • C09K2019/548—Macromolecular compounds stabilizing the alignment; Polymer stabilized alignment
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • G02F1/13345—Network or three-dimensional gels
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/13775—Polymer-stabilized liquid crystal layers
    • G02F2001/13345—
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/36—Micro- or nanomaterials

Definitions

  • the invention relates to and includes by reference Chinese patent application CN201611165277.5, which was filed on Dec. 16, 2016 and titled as ‘Temperature-controlled dimming film with a function of shielding near-infrared light and preparation method thereof’, and requires to enjoy the priority right of the above Chinese patent application.
  • the invention belongs to the field of functional liquid crystal material technology application, and particularly relates to a temperature-controlled dimming film with a function of shielding near-infrared light and a preparation method thereof.
  • Intelligent and controllable sunshade film is an important development direction in the field of energy-saving building materials.
  • the intelligent and temperature-controlled liquid crystal dimming film has the characteristic of automatically adjusting its light transmittance according to external temperature change, that is, when the weather is cold, the film is transparent, which does not affect indoor lighting and heating; when the weather is hot, the film automatically becomes into a light scattering state, which can shield most of the radiant energy of visible light and prevent indoor people's eyes from receiving strong sunlight.
  • the higher polymer content inside the film endows the film with a good bond strength, which is convenient for large-scale processing. Therefore, the intelligent and temperature-controlled liquid crystal dimming film has a good application prospect in the building energy-saving field.
  • An object of the present invention is to provide a temperature-controlled dimming film with a function of shielding near-infrared light, which has good transmittance and near-infrared light shielding effect at low temperatures, and automatically becomes into a light scattering state and simultaneously shields 90% of near-infrared light at high temperatures.
  • Another object of the present invention is to provide a method for preparing the temperature-controlled dimming film as above.
  • the invention provides a temperature-controlled dimming film with a function of shielding near-infrared light, which comprises a polymer network skeleton and liquid crystal molecules, wherein the polymer network skeleton consists of a polymer-dispersed liquid crystal network structure and a polymer-stabilized liquid crystal network structure and comprises a polymer matrix with pores inside which polymer networks are vertically aligned; and the liquid crystal molecules are dispersed in the polymer network skeleton and have smectic (SmA)-cholesteric (N*) phase transition. Between the skeleton and the liquid crystal molecules, nanoparticles, having absorption at 800-3000 nm, are dispersed.
  • SmA smectic
  • N* cholesteric
  • the polymer network skeleton is prepared from polymerizable monomers through stepwise polymerization.
  • the stepwise polymerization and the ultraviolet stepwise polymerization as mentioned below mean that the polymerizable monomers are polymerized in a controlled manner in the system, which include ultraviolet-initiated pre-polymerization and electrified polymerization under the combined action of ultraviolet light and electric field.
  • the first ultraviolet-initiated polymerization enables polymerization between 10% ⁇ 90% of the non-liquid crystal polymerizable monomers and 0.1% ⁇ 90% of the liquid crystal polymerizable monomers in the system, so as to form a substrate with a certain viscosity and a preliminary polymer matrix with pores.
  • polymerization occurs inside the pores to form polymer networks which clearly are vertically oriented.
  • the stepwise polymerization may be controlled by controlling the degree of the first ultraviolet-initiated polymerization.
  • the control can be achieved by choosing either extending or shortening the ultraviolet radiation period.
  • the first ultraviolet radiation period is chosen within 10-600 s.
  • the optional first ultraviolet radiation period may be 10-30 s, 30-60 s, 60-120 s, 100-200 s, 200-400 s, 400-600 s.
  • such a preliminary polymerization product that, the non-liquid crystal polymerizable monomer has a polymerization degree (monomer reaction ratio) of 10-20%, 20-30%, 30-50%, 50-60%, 60-70%, 70-90% and the liquid crystal polymerizable monomer has a polymerization degree (monomer reaction ratio) of 0.1-10%, 10-20%, 20-40%, 40-60%, 60-70%, 70-90%, can be obtained.
  • the methods of controlling the ultraviolet radiation period were used to control the stepwise polymerization. However it is known by those skilled in the art that other methods that can control polymerization progress may also be used to carry out the present invention.
  • the polymer matrix has a pore size of 1 um ⁇ 100 um, which may be adjusted as needed.
  • the vertically oriented polymer network prepared according to the method of the present invention may also be changed by controlling the pore size.
  • the pore size can be chosen from various ranges such as 1-10, 10-20, 20-40, 40-60, 60-80, 80-100 micron. Subject to the pore size, the corresponding vertically oriented polymer network will also be reduced into a smaller size.
  • the liquid crystal material, the polymerizable monomers, and the nanoparticles in the raw materials to prepare the dimming temperature-controlled dimming film are in a ratio by weight shown as below:
  • the liquid crystal material is a liquid crystal material having SmA ⁇ N* phase transition and its phase transition temperature is ⁇ 10° C. or higher.
  • the liquid crystal material comprises one or more selected from a liquid crystal material having smectic phase, a liquid crystal material having nematic phase, and a chiral compound.
  • the liquid crystal monomers of the liquid crystal material include, but not limited to, one or more selected from the following molecules:
  • the nematic liquid crystal material may also be selected from, but not limited to, commercially available liquid crystal materials, such as SLC-1717, SLC-7011, TEB30A etc. of Yongsheng Huaqing Liquid Crystal Material Co., Ltd., or E7, E44, E48 ZLI-1275, etc. of Merck Liquid Crystal Materials Co., Germany.
  • commercially available liquid crystal materials such as SLC-1717, SLC-7011, TEB30A etc. of Yongsheng Huaqing Liquid Crystal Material Co., Ltd., or E7, E44, E48 ZLI-1275, etc. of Merck Liquid Crystal Materials Co., Germany.
  • the chiral compound includes, but not limited to, one or more of the following molecules, such as cholesteryl nonanoate, CB15, C15, 5811, R811, S1011, R1011, and the like.
  • the nanoparticles comprise one or more selected from indium tin oxide (ITO), antimony tin oxide (ATO), tungsten trioxide (WO 3 ), molybdenum trioxide (MoO 3 ), tungsten bronze (alkali metal-doped WO 3 ) or copper sulfide (CuS) with oxygen defects.
  • ITO indium tin oxide
  • ATO antimony tin oxide
  • WO 3 tungsten trioxide
  • MoO 3 molybdenum trioxide
  • tungsten bronze alkali metal-doped WO 3
  • CuS copper sulfide
  • the liquid crystal material comprises a liquid crystal composition which comprises a first component, and one or more selected from a second component, a third component, a fourth component, and a fifth component.
  • the first component is one or more liquid crystal compound(s) selected from either one of the following Group A and Group B, or a mixture comprising one or more of Group A and one or more of Group B.
  • Group A represents liquid crystal compounds shown as Formula (1-a); and
  • Group B represents liquid crystal compounds shown as Formula (1-b), wherein R a is an alkyl group having 8 ⁇ 12 carbons atoms, and R b is an alkyl group having 8 ⁇ 10 carbon atoms;
  • the second component is one or more liquid crystal compound(s) selected from either one of Group C or Group D, or a mixture of one or more of Group C and one or more of Group D; wherein R c is an alkyl group having 6 ⁇ 7 carbon atoms, R d is an alkyl group having 5 ⁇ 7 carbon atoms.
  • Group C represents liquid crystal compounds shown as Formula (2-c); and
  • Group D represents liquid crystal compounds shown as Formula (2-d).
  • the third component is a liquid crystal compound shown as Formula (3); wherein R 3 is an alkyl group having 5 ⁇ 7 carbon atoms;
  • the fourth component is one or more liquid crystal compound(s) selected from any one of Group E, Group F and Group G, or a mixture of one or more of Group E, one or more of Group F, and one or more of Groups G; wherein R 4 is an alkyl Group having 5 ⁇ 7 carbon atoms.
  • Group E represents liquid crystal compounds shown as Formula (4-e);
  • Group F represents liquid crystal compounds shown as Formula (4-f);
  • Group G represents liquid crystal compounds shown as Formula (4-g);
  • the fifth component is chiral compounds having the same chiral configuration.
  • the liquid crystal composition comprises 15% ⁇ 40% of the first component, 35% ⁇ 60% of the second component, 1% ⁇ 10% of the third component, 5% ⁇ 25% of the fourth component and 1% ⁇ 20% of the fifth component.
  • the liquid crystal composition comprises the compounds shown as Formula (1-a), Formula (1-b), Formula (2-c), Formula (2-d), Formula (3), and Formula (4-e), Formula (4-f), Formula (4-g), and the fifth component.
  • the liquid crystal compound shown as Formula (1-a) has a mass fraction of 15% ⁇ 40%; the liquid crystal compound shown as Formula (1-b) has a mass fraction of 0% ⁇ 8%; the liquid crystal compound shown as Formula (2-c) has a mass fraction of 16% ⁇ 45%; the liquid crystal compound shown as Formula (2-d) has a mass fraction of 15% ⁇ 28%; the liquid crystal compound shown as Formula (3) has a mass fraction of 1% ⁇ 10%; the liquid crystal compound shown as Formula (4-e) has a mass fraction of 5% ⁇ 25%; the liquid crystal compound shown as Formula (4-f) has a mass fraction of 0% ⁇ 6%; and liquid crystal compound shown as Formula (4-g) has a mass fraction of 0% ⁇ 5%, and the fifth component has a mass fraction of 1% ⁇ 20%.
  • the polymerizable monomers used in the present invention are ultraviolet-polymerizable monomers, including non-liquid crystal ultraviolet-polymerizable monomers and liquid crystal ultraviolet-polymerizable monomers.
  • the non-liquid crystal ultraviolet-polymerizable monomers can be selected from, but not limited to, one or more of the followings, such as unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, epoxy acrylate, a polyene mercaptan system, polyether acrylate, aqueous acrylate, vinyl ethers, and the like.
  • the liquid crystal ultraviolet-polymerizable monomers can also be selected from, but not limited to, one or more of the following molecules, such as
  • m and n represent 4 ⁇ 8, x and y represent 1 ⁇ 2, and E and Q represent acrylate, epoxy acrylate, urethane acrylate, or epoxy or polyene mercaptan.
  • the nanoparticles are grafted with surfactant on their surfaces.
  • the temperature-controlled dimming film can shield 80% or more of near-infrared light and has a transmittance higher than 75% in visible light waveband while existing at a temperature lower than the phase transition temperature of the liquid crystal, and has a transmittance lower than 10% in both the visible and near-infrared light wavebands while existing at a temperature higher than the phase transition temperature of the liquid crystal.
  • the invention also provides a method for preparing the temperature-controlled dimming film, which comprises the steps of:
  • polymerization between parts of the non-liquid crystal photopolymerizable monomers are a small portion of the liquid crystal photopolymerizable monomers is induced by ultraviolet.
  • the surfactant is grafted on the surfaces of the nanoparticles by a microemulsion method, a reversed-phase microemulsion method or a surfactant method.
  • the temperature-controlled dimming film was prepared by the following typical method.
  • Step 1 A liquid crystal material having a suitable temperature range and phase transition temperature was selected.
  • Step 2 The nanoparticles were placed into a certain amount of solvent such as acetone or ethanol, etc. (about 1 mL of solvent per 4 mg of nanoparticles), and dispersed thoroughly in the solvent by ultrasonic for about 30 minutes.
  • solvent such as acetone or ethanol, etc.
  • Step 3 The liquid crystal of Step 1, polymerizable monomers, spacer particles, and an accelerator/initiator were mixed evenly. Afterwards, the nanoparticle dispersion of Step 2 was added to the mixture system in a certain ratio. The solvent in the nanoparticle dispersion was removed by heating or distillation or the like. As a result, a dispersion of the nanoparticles in the mixture system was obtained.
  • Step 4 The dispersion of the nanoparticles in the mixture system obtained in Step 3 was placed between the two conductive films and extruded into a film. At first, the polymerizable monomers in the system were partially polymerized, and then, as an electric field was applied to the film, the remaining polymerizable monomers were polymerized completely. As a result, a temperature-controlled dimming film with a function of shielding near-infrared light was prepared.
  • Specific surface modification methods include a microemulsion method, a reversed-phase microemulsion method, a microcapsule method, a coupling agent method, a surfactant method, a ligand exchange method, and the like. After the surface modification, the nanoparticles used in the present invention still have good dispersibility even when its content reaches 30% in the mixture system.
  • a stepwise ultraviolet-polymerization method is utilized to construct a polymer-dispersed and polymer-stabilized liquid crystal system (PD&SLC), in which a polymer-dispersed liquid crystal (PDLC) is combined with a polymer-stabilized liquid crystal (PSLC), inside the film.
  • PDLC polymer-dispersed liquid crystal
  • PSLC polymer-stabilized liquid crystal
  • the nanoparticles with strong shielding effect in the near-infrared waveband of 800 nm ⁇ 3000 nm are surface-modified and then doped at a certain ratio into the temperature-controlled liquid crystal dimming film, which greatly improves the film's shield performance in the near-infrared waveband.
  • the film prepared as above while exiting at a temperature lower than the phase transition temperature of the liquid crystal, shields 80% or more of near-infrared light and allows most of the visible light passing through; whereas, while existing at a temperature higher than the phase transition temperature of the liquid crystal, has an infrared light shielding rate up to 90% or higher and allows most visible light passing through in the form of scattered light, so as to ensure a good transmittance for visible light, but also prevent the indoor people's eyes from being irritated by strong sunlight.
  • the nanoparticles have good dispersibility in the liquid crystal/polymer composite material. When the film is at a low temperature, the transmittance of visible light can exceed 75%. In other words, when the film is transparent, the doped nanoparticles do not affect the transmission of visible light.
  • FIG. 1 demonstrates a near-infrared light absorption spectrum of the nanoparticles used in Example 1;
  • FIG. 2 is a curve graph showing the transmittance of the film prepared in Example 1 as a function of temperature
  • FIG. 3 demonstrates a visible-near-infrared spectrum of the film prepared in Example 1;
  • FIG. 4 demonstrates a near-infrared light absorption spectrum of the nanoparticles prepared in Example 2;
  • FIG. 5 is a curve graph showing the transmittance of the film prepared in Example 2 as a function of temperature.
  • FIG. 6 demonstrates a visible-near-infrared spectrum of the film prepared in Example 2.
  • FIG. 7 shows a Scanning Electron Microscope image of the cross section of the film prepared in Example 2.
  • the degree of preliminary polymerization may be controlled by other methods, and the difference in the polymerization degree endows the products with different properties, so that products may be prepared for different uses.
  • the selected liquid crystal material (LC) having smectic phase (SmA) to cholesteric phase (N*) transition was a liquid crystal material which had adjustable transition temperature and its phase transition temperature was SmA-35° C.-N*-80° C.-I, i.e., when the external temperature was lower than 35° C., the film was in a transparent state; whereas, when the film was at a temperature higher than 35° C., it was in a light scattering state.
  • Various commercially available materials satisfying the foregoing requirements can be used in the present invention. Those skilled in the art may also choose the compounds from those selected in the Summary of the Invention or a combination thereof.
  • PEDGA600 Polyethylene glycol diacrylate
  • Bis-EMA15 (Bisphenol a ethoxylate dimethacrylate) is
  • the nanoparticles used in this Example were ITO nanoparticles, which were purchased from Shanghai Huzheng Nano Technology Co., Ltd. Its absorption spectrum in the near-infrared waveband is shown as FIG. 1 .
  • Those skilled in the art may also choose other nanoparticles which have been reported in the prior art to use in the present invention.
  • CN105219091A disclosed copper sulfide nanoparticles
  • CN103724854B disclosed an infrared absorption material, both of which can be used to prepare the film of the present invention.
  • the names and ratios of the selected liquid crystals, polymerizable monomers, initiator, and spacer particles are listed in Table 2.
  • the components in Table 2 were mixed according to their ratios, and stirred at room temperature to form isotropic liquid.
  • the isotropic liquid was mixed evenly. And the total mass of the mixture was 19 g.
  • Step one The nanoparticle dispersion obtained in Step one was added to the mixture of Step two, and sonicated again for 10 minutes to disperse the nanoparticles evenly. The dispersion was then incubated at 80° C. for 24 h to completely remove the ethanol solution. As a result, a dispersion of ITO nanoparticles in the mixture system was obtained.
  • the dispersion of ITO nanoparticles in the mixture system obtained above was applied between two plastic films coated with indium tin oxide (ITO) transparent conductive films, and rolled to form a film.
  • the film was irradiated at room temperature by ultraviolet light having a wavelength of 365 nm and an intensity of 0.5 mw/cm 2 for 90 s. Then, the film was fabricated with electrodes; a voltage of 50.0 Hz, 170 v was applied; and the irradiation by 365 nm ultraviolet light was continued to obtain the temperature-controlled dimming film.
  • a temperature-variable ultraviolet-visible-near-infrared spectrophotometer was used to measure the light transmittance, when the film was kept at room temperature and at 40° C.
  • the external light intensity was 1.5 mw/cm 2
  • the irradiation period was 10 min. Therefore, a curve graph showing the transmittance of the film with a function of shielding near-infrared light prepared in Example 1 as a function of wavelength was obtained, as shown in FIG. 2 .
  • the test wavelength range was from 400 nm to 3000 nm.
  • ITO nanoparticles Due to the good conductivity, if ITO nanoparticles are added in a large amount, the electrodes are easily ablated when a voltage is applied to the film. Therefore, in this Example, the ITO nanoparticles were coated with a layer of silicon dioxide, which had no impact on the near-infrared absorption characteristics of the ITO nanoparticles, but insulated the nanoparticles from each other, so as to avoid ablation of the electrodes during power-up. The specific process was shown as follows: 2,3-nonylphenol polyether was added to 20 mL of cyclohexane solvent obtained in Step one, to construct a reversed-phase microemulsion system.
  • FIG. 5 shows the absorption spectrum of the nanoparticles in the near-infrared region.
  • the names and ratios of the selected liquid crystals, polymerizable monomers, initiator, and spacer particles are listed in Table 3.
  • the components in Table 3 were mixed according to their ratios, and stirred at room temperature to form isotropic liquid.
  • the isotropic liquid was mixed evenly.
  • the total mass of the mixture was 900 mg.
  • Step two The nanoparticle dispersion obtained in Step two was added to the mixture of Step three, and sonicated again for 10 minutes to disperse the nanoparticles evenly. The dispersion was then incubated at 80° C. for 24 h to completely remove the ethanol solution. As a result, a dispersion of ITO nanoparticles in the mixture system was obtained.
  • the dispersion of ITO nanoparticles in the mixture system obtained above was applied between two plastic films coated with indium tin oxide (ITO) transparent conductive films, and rolled to form a film.
  • the film was irradiated at room temperature by ultraviolet light having a wavelength of 365 nm and an intensity of 0.5 mw/cm 2 for 90 s.
  • the film was fabricated with electrodes; a voltage of 50.0 Hz, 170 v was applied; and irradiation by ultraviolet light having a wavelength of 365 nm and an intensity of 1.5 mw/cm 2 was continued for 10 min.
  • the intelligent temperature-controlled dimming film with a function of shielding near-infrared light of Example 2 was obtained.
  • a temperature-variable ultraviolet-visible-near-infrared spectrophotometer was used to test the curve graph of transmittance as a function of wavelength, when the film was at room temperature and at 40° C. respectively, as shown in FIG. 4 .
  • the test wavelength range was from 400 nm to 3000 nm.
  • the network morphology of the cross section of the film was observed, which clearly showed that a vertically oriented polymer network structure was formed inside the porous PDLC network structure (as shown in FIG. 5 ).

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